Catalytic roles of the acid sites in different pore channels of H‐ZSM‐5 zeolite for methanol‐to‐olefins conversion

H‐ZSM‐5 zeolite is a typical catalyst for methanol‐to‐olefins(MTO)conversion.Although the performance of zeolite catalysts for MTO conversion is related to the actual location of acid sites in the zeolite framework,the catalytic roles of the acid sites in different pore channels of the H‐ZSM‐5 zeolite are not well understood.In this study,the MTO reaction network,involving the aromatic cycle,alkene cycle,and aromatization process,and also the diffusion behavior of methanol feedstock and olefin and aromatic products at different acid sites in the straight channel,sinusoidal channel,and intersection cavity of H‐ZSM‐5 zeolite was comparatively investigated using density functional theory calculations and molecular dynamic simulations.The results indicated that the aromatic cycle and aromatization process occurred preferentially at the acid sites in the intersection cavities with a much lower energy barrier than that at the acid sites in the straight and sinusoidal channels.In contrast,the formation of polymethylbenzenes was significantly suppressed at the acid sites in the sinusoidal and straight channels,whereas the alkene cycle can occur at all three types of acid sites with similar energy barriers and probabilities.Consequently,the catalytic performance of H‐ZSM‐5 zeolite for MTO conversion,including activity and product selectivity,can be regulated properly through the purposive alteration of the acid site distribution,viz.,the location of Al in the zeolite framework.This study helps to elucidate the relation between the catalytic performance of different acid sites in the H‐ZSM‐5 zeolite framework for MTO conversion,which should greatly benefit the design of efficient catalyst for methanol conversion.

HZSM-35 zeolite catalyzed aldol condensation reaction to prepare acrylic acid and its ester:Effect of its acidic property

Acrylic acid(AA)and its ester,methyl acrylate(MA),were produced by a green one‐step aldol condensation reaction of dimethoxymethane and methyl acetate.The reaction was conducted over ZSM‐35 zeolites with different concentrations of Bronsted acid,which were prepared by the sodium ion‐exchange process with H‐form zeolite.The acidic property of HZSM‐35 was studied in detail through infrared experiments.About 51%of all bridging OH groups were distributed in cages,while 23%and 26%,respectively,were distributed in 10‐and 8‐ring channels.The catalytic performance was enhanced by a high concentration of Bronsted acid,indicating that Bronsted acid is an active site for the aldol condensation reaction.The ZSM‐35 zeolite possessing a concentration of Bronsted acid as high as 0.049 mmol/g demonstrated excellent performance with a MA+AA selectivity of up to 73%.

ADSORPTION EQUILIBRIUM OF ETHYLENE-CARBON DIOXIDE MIXTURE ON ZEOLITE ZSM5 AND ITS CORRELATION

Binary gas mixture adsorption equilibrium data for the ethylene-carbon dioxide system were obtained for cation exchanged forms of ZSM5 (Li^+, Na^+, K^+, Rb^+, Mg^(+2), Ca^(+2), Sr^(+2), and Ba^(+2)) for the gas phase CO_2 mole fracion of 0.766 at 308K and 101. 3kPa. The experimental adsorption phase diagrams were obtained for CO_2-C_2H_4 on NaZSM5 and MgZSM5. Single component adsorption isotherms for CO_2 and C_2H_4 were also obtained for these two zeolites. The single component data were used to obtain parameters derived in the vacancy solution model (VSM) and the statistical thermodynamic model(STM). These parameters were, in turn, used to predict binary mixture isotherms for these two zeolites. The agreement between experimental data and predicted value is generally good.

External surface modification of as-made ZSM-5 and their catalytic performance in the methanol to propylene reaction

Post-synthetic treatment of high-silica as-made ZSM-5 with organic template in the micropores was explored to reduce/remove the external surface acid density of ZSM-5. It is found that Na_2H_2 EDTA treatment can selectively remove the surface Al atoms, but generates new acid sites（likely silanol nests） on the external surface. H_3PO_4 treatment is unable to remove surface Al atoms, while small amount of P is left on the external surface, which effectively decreases the acid density. The catalytic performance of the resultant materials is evaluated in the methanol conversion reaction. H_3PO_4 treatment can effectively improve both the catalytic lifetime and the stability of propene selectivity.This occurs due to a combination of the increased tolerance to the external coke deposition and the depressed coking rate（reduced side reactions）. Na_2H_2 EDTA treatment only prolongs the catalytic lifetime, resulting from the improved tolerance to the external coke deposition. Under the optimized H_3PO_4 treatment condition, the resultant ZSM-5 gives a catalytic lifetime of about 1.5 times longer than the precursor. Moreover, the propene selectivity is improved, showing a slight increasing trend until the deactivation.

Thermodynamic study of direct amination of isobutylene to tert-butylamine

On basis of thermodynamic empirical equations, the thermodynamic parameters for the direct amination of isobutylene to tert‐butylamine, an atomically economic and green chemical reaction,were calculated. In particular, the equilibrium conversion of isobutylene under various reactionconditions close to those used in industry was calculated and discussed. Isobutylene amination is atemperature sensitive reaction due to its exothermic nature and isobutylene equilibrium conversiondecreases with temperature. However, kinetically, the amination reaction will be faster at ahigher temperature. Thus, there must be an optimum temperature for the reaction. A high pressureand n(NH3)/n(i‐C4H8) molar ratio promote the transformation of isobutylene to tert‐butylamine.Developing a highly efficient catalyst under mild reaction conditions is preferred for the aminationprocess. The reaction was investigated over a series of acidic zeolites. ZSM‐11 zeolite exhibited thebest performance with 14.2% isobutylene conversion (52.2% of the equilibrium conversion) and >99.0% tert‐butylamine selectivity. The effect of reaction conditions on the performance of the ZSM‐11 catalyst agreed with the thermodynamic results, which provides guidance for further catalyst development and reaction condition optimization.

Gas-Phase Beckmann Rearrangement of Cyclohexanone Oxime over B-ZSM-5 Derived Titanosilicalite

Four different ZSM 5 zeolites are tested for the gas phase Beckmann rearrangement of cyclohexanone oxime (CHO) into lactam. B ZSM 5 derived titanosilicalite (Ti ZSM 5) exhibits catalytic performances comparable to hydrothermally synthesized titanosilicalite (TS 1), much better than B ZSM 5 and Al ZSM 5. The effect of reaction conditions (solvent, feed space velocity, and water) on the catalytic performance of Ti ZSM 5 is studied. It is found that a quantitative relationship exists among the feed space velocity, the reaction time, and the CHO constant conversion. Ethanol or methanol as solvent shows higher activity, lactam selectivity, and stability than benzene and n hexanol. The addition of water to the rearrangement with a maximum amount of 1.0 mole per mole CHO results in the increase of CHO conversion while no meaningful changes in lactam selectivity and stability are observed.